Process of dyeing textile fibres using a phenyl sulphone dyeing assistant



United States Patent Office 3,536,438 Patented Oct. 27, 1970 3,536,438 PROCESS OF DYEING TEXTILE FIBRES USING A PHENYL SULPHONE DYEING ASSISTANT Hans-Peter Baumann, Munchenstein, and Robert-Christian Keller, Basel, Switzerland, assignors to Sandoz Ltd., Basel, Switzerland, a corporation of Switzerland No Drawing. Filed Mar. 3, 1967, Ser. No. 620,232 Claims priority, application Switzerland, Mar. 11, 1966, 3,576/66 Int. Cl. D06p 3/82 US. Cl. 8-21 14 Claims ABSTRACT OF THE DISCLOSURE BACKGROUND OF THE INVENTION Polyamide fibres can be dyed with anionic dyestuffs, but frequently the resulting dyed goods have a stripy or ringy appearance due to an uneven adsorption and distribution of dye. Furthermore, mixtures of polyamide fibres and elastomeric polyurethane fibres or yarns as are used for making woven or knitted fabrics cannot easily be level dyed in equal colour shades with anionic dyestuffs as these are preferentially adsorbed on the polyamide fibres, thus leaving the polyurethane fibres in a much paler shade and causing the fabrics to be stripy.

It has previously been proposed to use certain levelling agents to minimize the above difficulties, but these previously proposed levelling agents have not been entirely satisfactory for use or more of the following reasons: insufficient penetration power, necessity to effect a relatively troublesome separate treatment before dyeing, relatively high price of the levelling agent, and difficulties in handling these due to their being non-solids at ambient temperature.

We have now found that the use of certain sulphonated phenyl sulphones described hereinafter and which have an excellent penetration power enables one to dispense with a separate pretreatment before dyeing and to use relatively inexpensive products which, moreover, can be handled very easily because they are obtainable in the solid state at room temperature.

SUMMARY OF THE INVENTION The present invention provides a process for dyeing with anionic dyestuffs textile fibres of polycondensation products containing carbonarnide groups, which have varying affinity to anionic dyestuffs, characterized in that the fibres are treated with an aqueous solution of a phenyl sulphone optionally substituted and containing at least one 40 (cation) radical attached to an aromatic nucleus and at least one radical of the formula wherein X represents -O or S- and R represents a hydrogen atom or low molecular weight alkyl radical optionally substituted, a phenyl-, phenylalkylor diphenyl radical optionally substituted or an ortho-phenylyl radical optionally substituted which forms a furan or thiophene ring with the benzene ring adjacent to X, or of a condensation product thereof with formaldehyde or a nitrogen containing polyfunctional connecting agent containing at least one methylol radical DETAILED DESCRIPTION Examples of suitable cations, due to whose presence the sulphonated phenyl sulphones are rendered water soluble, are H alkali metal ions, preferably Na+ and K'*, further Mg++, Ca++, NH,+ and amines, for instance 3 3 3)2 2 3)3 2 5- s HOC H NH (HOC H NH (HOC H NH+ and others more.

The radical R-X in the phenyl sulphones is preferably an RO radical, wherein R has the above significance, and especially an R O- radical, wherein R is a hydrogen atom or a low molecular weight alkyl radical which may be substituted, or an optionally substituted phenyl-, phenylalkylor diphenylyl radical; examples of -O-R are therefore OH, OCH OC H Ophenyl, Obenzyl, O diphenyl,

wherein n is from 1 to 3, further wherein alky contains 2 to 5 carbon atoms, or

The preferred meaning of OR however, is OH, O-phenyl or O-diphenylyl.

The sulphonated phenyl sulphones used in the dyeing process of the invention are agents which are capable of regulating the speed of adsorption and distribution of anionic dyestuffs on the fibres to be dyed.

By anionic dyestuffs are designated dyestuffs which are capable of forming coloured anions in aqueous dye liquors, for example acid level dyestuffs, fulling dyestuffs, 1:1- and 1:2-metal complex dyestuffs, chrome dyes, direct dyes and reactive dyes.

Textile fibres of polycondensation products containing carbonarnide radicals and having varying affinity to anionic dyestuffs include synthetic polyamide fibres or polyurethane fibres becoming stripy or ringy on dyeing and mixtures of these fibres. Examples of polyamide fibres are nylon 6, 66, 610 6/66, 11, etc.; examples of polyurethane fibres are polycondensation products of diols and diisocyanates, e.g., of 1,4-butane diol and 1,6-hexamethylene-diisocyanate, or mixed condensation products of polyethers or polyesters with diisocyanates and diamines or hydrazine [Ullmann Enzyklopadie der technischen Chemie 14, 338,363, especially 351-2 (1963)].

The new dyeing process is especially suitable for dyeing mixtures of synthetic polyamide fibres and elastomeric fibres of polyurethanes. Such mixtures have become increasingly more important in the last few years. Taken individually, both kinds of fibres are capable of being dyed with anionic dyestuffs. However, simultaneous dyeing of polyamide and elastomeric fibres with anionic dyestuffs entails difficulties, as the dyestuffs are not built up in the same way on both kinds of fibres. Mostly the polyamide fibre part becomes dyed quicker and in a deeper shade than the elastomeric fibre portion. It is therefore not easily possible to achieve an equal shade or level tint on dyeing these two kinds of fibres simultaneously, for example a dyeing in a uniform shade, or to obtain a darker shade with the elastomeric fibres than with the polyamide fibres.

'Elastomeric or spandex fibres 'have a high elasticity and the fibre forming substance is a chain-like polymer which mainly consists of segmented polyurethane. These fibres are produced and sold commercially under various trade names [for these trade names see, e.g., H. U. Schmidlin, SVF-Fachorgan 20, (1965) No. 2, page 8].

Threads or yarns containing a portion of spandex fibres are commercially available, for example, under the name of corespun yarns in the production of which endless elastomeric threads are wrapped round with polyamide staple yarns; alternatively they are available as staple fibres which are obtained by spinning polyamide staple fibres with cut elastomeric threads.

Suitable synthetic polyamide fibres which may be dyed together with elastomeric fibres include the most varied fibres consisting of synthetic polyamide and also such as are subjected to a special treatment, e.g. texturizing. Such products are known, for example, under the following names some of which are registered: nylon 6, nylon 6.6, nylon 66/6, nylon 10, Grilon, Perlon, Mirlon, Enkalon, Tastan, Stylon, Rilsan, Ban-Ion, Dederon, etc.

The fibres or fibre mixtures to be dyed in accordance with the process of the invention, preferably those of elastomer and polyamide fibres, may take any desired form, for example free fibres, threads, woven or knitted fabrics, or made up goods, e.g. Pullovers, articles of fashion, shirts and sports clothing.

The optionally substituted phenyl sulphones to be used in accordance with the invention and containing at least one aromatically linked SO (cation)-radical and at least one radical of the formula RX-, wherein R and X have the above significance, may be obtained in accordance with known methods. Suitable one uses as starting material a compound of the formula wherein A is a phenyl radical optionally substituted with one or more halogen atoms, hydroxy radicals, alkyl radicals containing 14 carbon atoms, or a diphenylyl radical, and X and R have the above significance, or a mixture of two or more such compounds and converts to the corresponding monosulphonic acid. Conversion of-the last mentioned to the corresponding phenyl sulphone containing sulphonic acid radicals may be effected, for example, by heating to 100-200 C. at a reduced pressure; the resulting product is soluble in water in the form of the alkali metal salt. The phenyl sulphone, depending on the nature of the starting material and the reaction conditions, contains one or more SO radicals per molecule. In general, the phenyl sulphones to be used in accordance with the invention are mixtures of monoand poly-(phenyl sulphones), e.g. of mono-, di-, tri-, tetra-, and penta- (phenyl sulphones), the average SO2-- radical content per molecule being preferably 1 to 3. Furthermore, other products usable in accordance with the invention are obtained when the resulting phenyl sulphones are additionally reacted with formaldehyde or with connecting agents containing methylol radicals, for example dimethylol urea.

Suitable compounds of the formula are, for example, phenol, 2-chlorophenol, 4-phenylphenol, 3-methylphenol, anisole, phenetole, diphenyl oxide, phenoxy diphenyl, diphenylsulphide, dibenzofuran and 3-hydroxydibenzofuran. The production of phenyl sulphones to be used in accordance with the invention is described, e.g., in German patent specifications Nos. 260,379; 265,- 415; 266,124; 266,139; 825,090 and 819,694. The conditions of dyeing are substantially those usual for the different types of anionic dyestuffs, e.g. temperatures of from to 140 C., preferably to C., and at super atmospheric pressure when the dyeing temperature exceeds 100 C.; bath liquor ratios of from 1:5 to 1:200, preferably of 1:10 to 1:100; pH values of 2 to 8, depending on the dyeing properties'of the dyestuffs used when the treatment of the fibres with the sulphonated phenyl sulphones is effected in the dye bath itself. However, the treatment with the sulphonated phenyl sulphones may be effected before the actual dyeing at temperatures of about 20 C. to 100 C., preferably at 50 to 100 C. and in slightly acid medium, e.g. acetic acid medium.

The fibres treated in this way may be removed from the treatment liquor, rinsed with water, if desired dried and then put in a freshly prepared dye bath and dyed therein, or may be dyed after treatment in the same liquor after the addition of a dyestuif and any dyeing assistants (salts, acids, metallizing agents, surface active agents, etc.).

The amount of sulphonated phenyl sulphone to be used in accordance with the process depends on the nature of the fibres to be dyed, on the quantity and structure of the dyestuff used for dyeing, the pH value of the dyeing liquor, the dyeing temperature and the duration of the obtained. It amounts to from 0.02 to 20% by weight, preferably 0.1 to 15% by weight, of the material to be dyed. In addition to the sulphonated phenyl sulphone to be used in accordance with the process of the invention, it is possible to add to the dye baths one or more buffer substances, e.g. hexamethylenetetra'mine, disodium phosphate, tetrasodium pyrophosphate, urea or ammonium rhodanide. If desired it is possible to use for dyeing also one or more non-ionogenic, anionic or cationic, capillary active compounds, providing this does not lead to the formation of a precipitate with the dyestuff and the sulphonated phenyl sulphone. The dyeing of, e.g. spandex/ nylon mixtures is advantageously effected in such a way that the phenyl sulphone to be used in accordance with the process of the invention is either added to the dye bath together with the dyestuff and dyeing is effected as usual, or the mixed material is first pretreated with a solution of the sulphonated phenyl sulphone, the dyestuff is then added and dyeing effected. However, it is likewise possible to proceed in such a way that the fibres, e.g. a mixture of elastomeric and synthetic polyamide fibres, are first subjected to a pretreatment with a solution of the sulphonated phenyl sulphone, the dyestuif is then added and dyeing effected. However, it is likewise possible to proceed in such a way that the fibres, e.g. a mixture of elastomeric and synthetic polyamide fibres, are first subjected to a pretreatment with a solution of the sulphonated phenyl sulphone and then dyed without intermediate drying in a freshly prepared dye bath.

The dyeing process in accordance with the invention can, however, likewise be effected in such a way that the synthetic polyamide is subjected to treatment with the sulphonated phenyl sulphone to be used in accordance with the process of the invention before processing to give a fibre mixture of elastomer-polyamide.

The sulphonated phenyl sulphone to be used in accordance with the process of the invention may be prepared, for example, in the following manner; the sulphones are mixtures constituted by monomers and polymers essentially having up to 5 recurring units, n thus being 0, 1, 2, 3 or 4 and Ph being the phenyl or phenylene radical respectively, n=1, 2 or 3 and m=1 or 2.

PHENYL SULPHONE A 102 parts of 100% sulphuric acid (1.04 mols) are slowly added to 94 parts of hydroxybenzene (1 mol) and heated for 4 hours to 100 C. Subsequently the pressure is reduced to 20 mm. of Hg, the temperature is increased during 2 hours to C. and condensation is effected for 4 hours at 160 C. The pressure is then further reduced to 3 mm. of Hg and the temperature is simultaneously increased to C. Condensation is then effected until a sample of the reaction mixture has an acid content of 340 mval./100 g. (titrated against Congo red).

The product has the formula:

PHENYL SULPHONE B 110 parts of 100% sulphuric acid (1.12 mols) are added dropwise to 170 parts of 1-hydroxy-4-phenylbenzene (1 mol) and heating for 4 hours to 100 C. is effected. Subsequently the reaction mixture is heated for 3 hours at 120 C. at a pressure of mm. of Hg, the temperature is increased to 160 C. and condensation at that temperature and pressure is effected until a sample of the reaction mixture has an acid content of 237 mval./ 100 g. (titrated against Congo red).

The product has the formula:

The following phenyl sulphones are produced in the same way:

MvaL/lOO g.

Phenyl sulphone Starting material C 1-hydroxy-3-methylbenzene D l-hydroxy-Z-chlorobennene the phenyl sulphone D has the formula: OH OH 166 parts of 60% oleum are added dropwise to 186 parts of hydroxybenzene (2 mols) and after completion of the sulphonation during about 2 hours heated to 180 C. at a pressure of 11 mm. of Hg. parts of hydroxybenzene (0.32 mol) are added to 157 parts of the resulting acid resin and heated to 175 C. for 3 hours. The pressure is then reduced to 16 mm. of Hg 'and the temperature kept at 175 C. until a sample of the resulting resin has an acid content of 145 mvaL/ 100 g. (titrated against Congo red). The formula of this product is similar to that of phenyl sulphone A.

PHENYL SULPHONE G 168 parts of diphenylene oxide (i.e. dibenzofuran) (1 mol) and 147 parts of 100% sulphuric acid (1.5 mols) are heated to 100 C. for 4 hours. Subsequently the temperature is increased during 2 hours to C. and condensation is first effected at 140 C. at a pressure of 13 mm. of Hg for 2 hours and then for a further 3 hours at C. at a pressure of 3 mm. of Hg. The resulting product has an acid content of 455 mval./100 g. of product (titrated against Congo red).

The light brown powdered sulphone has the following formula:

are an PHENYL SULPHONE H 184 parts of 3-hydroxy-diphenylene oxide of the formula are used and working is first effected in the same way as for the preparation of phenyl sulphone G. The melt is kept at C. at a pressure of 3 mm. of Hg until the acid content amounts to 350 mval./ 100 g. (titrated against Congo red).

The resulting product has the following formula:

net-tan PHENYL SULPHONE I 73.5 parts of 100% sulphuric acid (0.75 mol) are added to 46 parts of methylbenzene (0.5 mol) and heated to 100 C. until a sample is completely water soluble (about 1% hours). Then 170 parts of phenoxybenzene (1 mol) are added and heating to 160 C. for 4 hours is effected; subsequently the temperature is increased to C. during 4 hours, condensation is first effected for 1 hour at 200 C. and 15 mm. of Hg and then at 210 C. and 3 mm. of Hg until the resulting product has an acid content of 145 mval./10O g. of product (titrated against Congo red). The product has the formula:

PHENYL SULPHONE K PHENYL SULPHONE L 246 parts of a yellow brown oil having natural reaction, of which the main constituent is phenoxy-diphenyl (density of the oil: 1.139, solidification point: 0 C., boiling points: 270350 C.), with 148 parts of 100% sulphuric acid are heated at 100 C. for 4 hours. Subsequently the present is reduced to 17 mm. of Hg and the temperature is increased to 140 C. during 2 hours. The pressure is then further reduced to 2 mm. of Hg and the temperature increased to 150 C. Condensation is then effected until a sample of the condensate has an acid content of 350 mval./ 100 g. of resin (titrated against Congo red).

The sulphone has the following formula:

PHENYL SULPHONE M Working is effected as for the production of the phenyl sulphone K, but using 127.5 parts of diphenyl oxide and 70.5 parts of hydroxy benzene and the condensation is effected at 160 C. and 3 mm. of Hg until the acid content has fallen to 355 mvaL/ 100 g. of product (titrated against Congo red).

PHENYL SULPHONE N Working is effected as for the production of phenyl sulphone K, but using 186 parts of diphenyl sulphide. The resulting product has an acid content of 375 mval./ 100 g. (titrated against Congo red). The product has the formula:

PHENYL SULPHONE O 50 parts of the phenyl sulphone A are mixed with 10 parts of water and 23 parts of 30% sodium hydroxide solution and heated to 90 C. until dissolution has taken place. The solution is cooled to 50 C., a solution of 4.5 parts of dimethylol urea in parts of water is added and condensation for 13 hours is effected at temperatures between 50 and 60 C. Subsequently the solution is evaporated and a brownish powder results.

In the phenyl sulphones A to N the free sulphonic acid radicals are neutralized with concentrated sodium hydroxide solution and the solutions adjusted to a content of 5% in relation to the non-neutralized compounds. The phenyl sulphone O is neutralized with dilute sulphuric acid and the content brought to 5% based on the effective substance.

PHENYL SULPHONE P 3 parts of 100% sulphuric acid are added at room temperature to 25 parts of phenyl sulphone A (with an acid content as free acid of 340 mval./ 100 g.), heating is then effected to 140 and this temperature maintained for 1 hour. The mass is allowed to cool, neutralized with about 41 parts of 30% sodium hydroxide solution and evaporated to dryness. 40 parts of a light brown water soluble powder are obtained. The product has a similar formula to that of phenyl sulphone A, but at least one further H and in the Ph residue is replaced with -SO H.

Instead of the sodium hydroxide solution it is possible to use potassium or lithium hydroxide solution, sodium or potassium carbonate solution or even solid carbonates or bicarbonates of sodium, potassium or lithium. Furthermore, there may likewise be used as neutralization agent ammonia, magnesium oxide or carbonate, calcium oxide, hydroxide or carbonate, as well as solution of water soluble amines, for example methylamine, dimethylamine, trimethylamine, ethylamine, ethanolamine, diethanolamine, triethanolamine as well as the corresponding propanolamines and hexamethylenetetramine. Instead of sulphuric acid it is likewise possible to use other acids, for example hydrochloric acid, acetic acid, formic acid or even phosphoric acid as well as organic sulphonic acids (methane, benzene or 4-methylbenzene sulphonic acid).

The sulphones of the Formula A below, i.e. sulphones G to N above, are new; they are especially useful for dyeing harry-dyeing nylon and have the advantage of practically not foaming as do the known sulphonated diphenyl oxides which contain a long aliphatic chain; furthermore, the compounds (A) are very good dispersing agents in acid or neutral medium and also, in contrast to e.g. sodium dinaphthylmethanedisulphonate, in alkaline medium.

oom). iii-(sown)...

wherein X represents O- or -S, each of Z and Z represents a hydrogen atom or Z together with Z represents a single bond, and each of Z and Z represents hydrogen, halogen, lower alkyl or alkoxy, hydroxy, carboxy or optionally substituted phenyl, and each of p and q represents 1 or 2. i

In the following examples, which illustrate the process of the invention, the parts are by weight, the percentages are by weight and the temperatures are stated in degrees centigrade. The quantities of phenyl sulphones stated in the examples relate to the condensation products with freeSO Hradicals in the case of phenyl sulphones A to N, or as the neutralized effective substance in the case of phenyl sulphone 0.

EXAMPLE 1 A yarn consisting of 50 parts of nylon 6.6 and 50 parts of a spandex fibre Lycra [Ullmann 14351 (1963)] are dyed in 4000 parts of a dye bath containing the following ingredients: 0.25 part of sodium-1-amino-2-bromo-4- (4'-methyl-phenylamino)-anthraquinone 2 sulph onate (dyestuif I); 2 parts of acetic acid; and 1.6 parts of phenyl sulphone A.

The yarn is put into the dye bath at 35 and heating to 95 is eflected during 40 minutes. Dyeing at this temperature is effected for 1 hour. Both yarns are dyed level and in an even shade. When phenyl sulphone A is not added to the dye bath the dyestufi becomes preferentially adsorbed on the nylon 6.6 yarn and the Lycra yarn is dyed only in a pale shade.

An equally good result is obtained when the phenyl sulphone A is replaced with the same amount of one of the phenyl sulphones B, L or N.

EXAMPLE 2 50 parts of a nylon 6.6 yarn and 50 parts of a spandex fibre Lycra yarn are put in 3000 parts of a bath containing the following ingredients: 2 parts of 80% acetic acid; 2 parts of phenyl sulphone C. The yarn is put into the bath at 40 and the liquor is heated to and kept at this temperature for 10 minutes. The bath is then cooled to 50 and 0.25 part of the dyestuif (I) are added. The bath is then heated during 10 minutes to and dyeing at this temperature is effected for 1 hour. Both yarns are dyed level and in equal shade. When the phenyl sulphone C is not added to the dye bath the dye is preferentially adsorbed to the nylon 6.6 yarn and the Lycra yarn is dyed only in a pale shade.

Yarns likewise dyed level and in equal shade are obtained when 3 parts of phenyl sulphone E or 2 parts of one of the phenyl sulphones, G, H, K, M or O are used instead of the phenyl sulphone C.

9 EXAMPLE 3 A yarn of 50 parts nylon 6.6 and 50 parts of spandex fibre Lycra are put into 4000 parts of a liquor containing the following ingredients: 3 parts of 80% acetic acid; 2.5 parts of phenyl sulphone A. The material is put into the bath at 40, heating to 90 is effected and the liquor is kept for 20 minutes at this temperature. The bath is then cooled to 40 and 0.3 part of the sodium salt of l-hydroxy-2-(3'-phenylarninosulphonyl-4-methylphenylazo)-naphthalene-4-sulphonic acid (dyestuff II) are added. Subsequently heating to 95 is eifected for 40 minutes and dyeing at this temperature is eifected for 1 hour. They Lycra and the nylon 6.6 yarn are dyed in equal shade and level. When phenyl sulphone A is not added to the dye bath the dyestuif is mainly adsorbed on the nylon and the Lycra yarn is only dyed is a pale shade.

The 2.5 parts of phenyl sulphone A can be replaced without any difiiculty with 2 parts of phenyl sulphone B or 3 parts of phenyl sulphone L.

When, insted of the dyestutf (II), there is used the same amount of a green dyestuif of the formula SO Na (III) green dyeings are produced which are similarly level and of equal shade.

EXAMPLE 4 100 parts of the yarn mixture of Example 3 are treated in a solution of 2.5 parts of phenyl sulphone N and 2 The Lycra and nylon yarn become level dyed in an equal shade of green.

One obtains likewise a dyeing of equal shade when the pretreatment of the yarn mixture is effected with 12 parts of the phenyl sulphone A and the actual dyeing is eifected with 0.5 part of the dyestuff (IV Without pretreatment the majority of the dyestuff is adsorbed on the nylon fibre and the Lycra fibre is only dyed in a pale shade.

It is likewise possible to Work with less dye liquor, e.g. 4000 or 5000 parts of water, without adversely aifecting the results.

EXAMPLE 6 Working is effected in the manner described in Example 5 with 8 parts of phenyl sulphone B in the pretreatment liquor and 0.3 parts of the dyestutf having the formula are used. The Lycra yarn and the nylon yarn are dyed in an equal shade of blue, while without pretreatment the dyestuff is for the most part adsorbed in the nylon yarn and the Lycra yarn is only dyed in a pale shade.

EXAMPLE 7 A yarn consisting of 50 parts of nylon 6 and 50 parts of a spandex fibre named Lycra are put into 4000 parts of a liquor containing the following ingredients: 2 parts of 80% acetic acid; 4 parts of phenyl sulphone A. The yarns are put into the liquor at heating to 90 is effected and this temperature is maintained for 15 minutes. The bath is then cooled to 40 and 0.25 part of a red dyestutf parts of 80% acetic acid in 4000 parts of water for 15 40 having the formula EXAMPLE 5 100 parts of the yarn mixture of Example 3 are pretreated as in Example 3 with a solution of 2 parts of 80% acetic acid and 6 parts of the phenyl sulphone B in 6000 parts of water.

The bath is then cooled to 40 and 4 parts of ammonium sulphate and 0.25 part of the dyestuff of the are added thereto. The dye bath is then heated during minutes to 95 and kept for 2 hours at this temperature.

are added. During 45 minutes the bath is brought to 95 and dyeing at this temperature is elfected for 2 hours. The Lycra yarn is dyed in the same way as the nylon 6 yarn with the same colour shade. In contra-distinction to this, when the phenyl sulphone A is not present in the dye liquor, the Lycra yarn is dyed in a substantially paler shade than the nylon 6 yarn.

EXAMPLE 8 100 parts of the yarn mixture of Example 3 are put at 40 into 10,000 parts of a dye liquor containing the following ingredients: 0.2 part of the 1:2-chromium complex compound of l-(2-hydroxy-5-methylsulphonylphenylazo)-2-hydroxy-8-acetyl-amino naphthalene (dyestuif (VII)); 4 parts of ammonium sulphate; 1 part of acetic acid; and 3.6 parts of phenyl sulphone A.

The liquor is heated to during 45 minutes and dyeing at this temperature is effected for 1 hour. The Lycra and nylon yarn are dyed in an equal shade of grey. When the phenyl sulphone A is not added to the bath, the dyestutf after the dyeing process is mainly adsorbed on the nylon yarn and the Lycra yarn is only dyed in a pale shade.

When the phenyl sulphone A is replaced with 3 parts of the phenyl sulphone B, very good results are likewise obtained.

A very good result is also obtained when the yarn mixture is first treated at 50 for 10 minutes in a solution of 4 parts of one of the phenyl sulphones A or L or 3 1 1 parts of the phenyl sulphone N or 6 parts of one of the phenyl sulphones C, F or K and 1 part of 80% acetic acid in 10,000 parts of water and then 4 parts of ammonium sulphate and 0.2 part of dyestuff (VII) are added, the dye liquor is brought to 95 in 45 minutes and dyeing is effected for 1 /2 hours at 95l Obviously the dyeing in a lesser amount of dye liquor, e.g. 6000 or 4000 parts of water, can be carried out with an equally good result.

This dyeing method is also very suitable for the dyestulfs (IV), (V) or (VI).

EXAMPLE 9 100 parts of the yarn mixture of Example 3 are treated during 10 minutes at 50 in 4000 parts of a liquor which contains 1 part of ammonium sulphate and 6 parts of phenyl sulphone A. 0.1 part of the 1:2-chromium complex compound of l-phenyl-3-methyl-4 (2-carboxyphenylazo)-5-pyrazolone (dyestuff (VIII)) and 0.15 part of an anionic dispersing agent, e.g. sodium-di-naphthylmethanedisulphonate or sodium-1igninsulphonate, are added. The dye bath is then heated to 95 during 45 minutes and this temperature is maintained for 1 hour. After the dyeing the Lycra and nylon yarns are dyed in an equal shade of yellow. When the phenyl sulphone A is not added to the dye bath, the dyestuff is mainly adsorbed on the nylon and the Lycra fibre is dyed only in a pale shade.

Instead of using 6 parts of phenyl sulphone A it is possible to use with equal success 2.5 parts o'f phenyl sulphone B or 4 parts of phenyl sulphone L or N, or 6 to 8 parts of phenyl sulphone F or the ammonium sulphate is replaced with 1 part of 80% acetic acid.

The dyestuff (VII) gives a level dyeing in. an equal shade of grey.

EXAMPLE 10 100 parts of the yarn mixture of Example 3 are dyed in 4000 parts of a dye liquor containing the following ingredients: 0.25 part of the dyestuff of formula COONa COONa 110 4 parts of ammonium sulphate; 2 parts of 80% acetic acid; 1 part of one the phenyl sulphones G or H. The yarns are placed in the dye liquor at 40 and heating to 95 during 40 minutes is effected. Dyeing is effected at this temperature for 1 hour. Subsequently the liquor is cooled to about 70 and 3 parts of 85% formic acid and 1 part of potassium bichromate are added and heating is again effected to 95". This temperature is maintained for 1 hour. The Lycra and nylon yarns are then dyed in an equal shade of yellow. When the phenyl sulphone A is not added to the dye liquor, the nylon 6.6 after dyeing has a deeper dye shade than the Lycra fibre.

Equally good results are obtained when the phenyl sulphone A is replaced with 1 part of the phenyl sulphones B, D, F or 1 part of a 1:1 mixture of phenyl sulphones A and F or 0.5 part of one of the phenyl sulphones A and N.

EXAMPLE 11 100 parts of yarn mixture of Example 3 are treated in a liquor of 4000 parts of water, 2 parts of 80% acetic acid and 3 parts of phenyl sulphone A at 80 during 15 minutes. The bath is then cooled to 40 and 0.25 part of the sodium salt of l-hydroxy-2-phenylazo-6-(4",6"- dichloro-l",3"-5"-triazinyl-2"-amino) naphthalene-3,2- disulphonic acid (dyestuff X) and 0.25 part of a phosphate buffer of pH value 7.0 are added to the liquor. The liquor is then heated to 95 and dyed at this temperature for 1 /2 hours. After the dyeing the Lycra yarn is clearly dyed. When the phenyl sulphone A is not present in the 12 dye liquor, the Lycra yarn is dyed in only a very pale shade.

Equally good results are obtained with one of the phenyl sulphones B and 1.

EXAMPLE 12 A yarn consisting of 50 parts of nylon 6.6 and 50 parts of spandex fibre ESPA are treated at for 10 minutes in 5000 parts of a liquor containing the following ingredients: 2 parts of 80% acetic acid; and 2 parts of phenyl sulphone A. The liquor is then cooled to 40 and 0.25 part of dyestuff (I) are added. The bath is then heated to during 40 minutes and dyeing at this temperature is etfected for 1 /2 hours. The ESPA and nylon yarns are dyed level and in an equal shade. When the phenyl sulphone A is not present in the dye bath, the dyestuif is almost completely adsorbed to the nylon yarn and the ESPA fibre is dyed only in a pale shade.

When the phenyl sulphone A is replaced with 2 parts of one of the phenyl sulphones B and N or 3 parts of the phenyl sulphone E or 3.5 parts of the phenyl sulphone F or 4 parts of the phenyl sulphone D, very good results are likewise obtained.

EXAMPLE 13 parts of a material consisting of 20 parts of spandex fibre Blue C and 80 parts of nylon 6.6 fibre are put into 400 parts of a liquor containing the following ingredients: 2 parts of 80% acetic acid; and 3 parts of one of the phenyl sulphones K, L or M.

The material is put into the liquor at 50 and this temperature is kept for 15 minutes. Subsequently 0.25 part of dyestuff (I) are added to the liquor and this is heated to 95 for 45 minutes. This temperature is maintained for 1 hour. A level dyed material results of equal colour shade. When no phenyl sulphone is added to the bath the Blue C fibres are practically undyed. For this reason the material has an unattractive aspect. This is particularly noticeable when the material is stretched.

Equally good results are obtained when 2.5 parts of phenyl sulphone A or 2 parts of phenyl sulphone B or 6 parts of one of the phenyl sulphones G and H are used.

EXAMPLE 14 A yarn consisting of 50 parts of nylon 6.6 and 50 parts of spandex fibre Rhodastic are dyed according to the dye method of Example 2, however, with the difference that the pretreatment is effected with 8 parts of one of the phenyl sulphones A and B and the dyeing itself with 0.5 part of dyestutf (I). After dyeing for 2 hours the Rhodastic fibre is dyed in a deep shade, whereas it is dyed only in a pale shade without any phenyl sulphone.

E)QAMPLE 15 A yarn consisting of 50 parts of nylon 6.6 and 50 parts of spandex fibre Bayer-Elastomer is dyed according to the dye method of Example 2 using 1 part of phenyl sulphone A in the pretreatment bath. The nylon and spandex fibres are level dyed in an equal shade. When phenyl sulphone A is not present in the dye bath, the dyestuif is preferentially adsorbed on the nylon and the spandex fibre is dyed only in a pale shade.

Equally good results are obtained with 2 parts of one of the phenyl sulphones K and L. When the amount of phenyl sulphone A is increased to 6 parts and the dyestuff (I) is replaced with 0.5 part of dyestuif (VI), the spandex fibres are dyed in a noticeably deeper shade than the nylon, while in the absence of phenyl sulphone A the nylon is dyed in an appreciably deeper shade than the spandex fibres.

EXAMPLE 16 A yarn consisting of 50 parts of nylon 6 and 50 parts of a spandex fibre named Glospan is dyed according to the dye method of Example 2 using 1 part of one of the phenyl sulphones A and B. The Glospan and nylon yarns are dyed in an equal shade. When no phenyl sulphone is present in the dye bath, the dyestuif is mainly adsorbed on the nylon fibres and the Glospan yarn is dyed only in a pale shade. When, instead of the dyestuflf (I), there are used 0.25 part of the sodium salt of 1-[2-(4-methylphenyl sulphonyl) 4'-acetylamino-phenylazo]-2-amino- 8-hydroxy-naphthalene-6-sulphonic acid (dyestuff (XI)) are used and the amount of phenyl sulphone A is increased to 2 parts, there is likewise obtained a level dyeing of an equal violettish red shade.

EXAMPLE 17 50 parts of a yarn consisting of nylon 6.6 are put into 2000 parts of liquor containing the following materials: 1 part of 80% acetic acid; and 1 part of phenyl sulphone 4 A. The yarn is put into the liquor at 40 and heating to boiling for minutes is effected. The nylon yarn is then briefly rinsed with cold water and, together with 50 parts of a yarn consisting of spandex Lycra, put into 4000 parts of a fresh dye liquor containing 2 parts of 80% acetic acid and 0.25 part of dyestuif (I). The bath is heated to 95 during minutes and dyeing at this temperature is effected for 1 hour. The Lycra and nylon yarns are level dyed in an equal shade. When untreated nylon yarn is used for the dyeing, the Lycra yarn after the dyeing is dyed in a weak shade and the nylon yarn in a deep shade.

An equally good result is obtained when the pretreated nylon yarn is subjected to an intermediate drying at 80.

EXAMPLE 18 100 parts of a stripy dyeing nylon 6.6 material are dyed in 4000 parts of a dye liquor containing 0.3 part of sodium-l-amino-4-(4'-acetylaminophenylarnino) anthraquinone-2-sulphonate, dyestuff (XII), 4 parts of 85% formic acid and 1 part of phenyl sulphone G.

The material is put into a dye liquor at this is heated to 98 during 45 minutes and kept at 98l00 for 1 hour. The dyed material'is removed from the liquor, rinsed with water and dried. A level, stripe-free greenish blue dyeing results. With the same quantity of one of the phenyl sulphones H, K or L or with 2 parts of phenyl sulphone P it is likewise possible to obtain level, stripefree dyeings, while without phenyl sulphone the dyed material shows noticeable stripes.

Although the present invention is described herein with particular reference to specific details, it is not intended that such details shall be regarded as limitations upon the scope of the invention except insofar as included in the accompanying claims.

We claim:

1. A process for dyeing textile fibers of synthetic polyamide fibers, elastomeric polyurethane fibers and mixtures thereof with anionic dyestuffs which comprises treating said fibers before or during dyeing with an aqueous solution of a phenyl sulfone selected from the group consisting of:

OCHa 00113 a phenyl sulfone of the formula:

wherein X represents -O- or S, each of Z and Z represents a hydrogen atom or Z together with Z represents a single bond, and each of Z and Z represent hydrogen, halogen, lower alkyl alkoxy, hydroxy, carboxy, or phenyl and each of p and q represents 1 or 2.

2. A process according to claim 1, in which the treatment with the phenyl sulphones and the dyestuff is efiected in the same liquor.

3. A process according to claim 1, in which the treatment With the phenyl sulphone is effected before dyeing.

4. A process according to claim 1, in which the textile fibres to be dyed are a mixture of synthetic polyamide fibres and elastomeric polyurethane fibres.

5. A process according to claim 1, in which treatment is effected with a phenyl sulphone wherein n and m are 0 and 1 respectively.

6. A process according to claim 1, in which treatment is effected with a phenyl sulphone wherein n and m are greater than 0 and 1 respectively.

7. A process according to claim 1, wherein phenyl sulfone (a) is employed.

8. A process according to claim 1, wherein phenyl sulfone (b) is employed.

9. A process according to claim 1, wherein phenyl sulfone (c) is employed.

10. A process according sulfone (d) is employed.

11. A process according sulfone (e) is employed.

12. A process according sulfone (f) is employed.

13. A process according sulfone (g) is employed.

14. A textile fiber treated in accordance with the process of claim 1.

to claim 1, wherein phenyl to claim 1, wherein phenyl to claim 1, wherein phenyl to claim 1, wherein phenyl References Cited UNITED STATES PATENTS 2,623,806 12/1952 Fuchs 821 3,118,723 1/1964 Harding. 3,199,942 8/1965 Kuth et al. 3,290,111 12/1966 Hees et al. 889 X GEORGE F. LESMES, Primary Examiner T. J. HERBERT, JR., Assistant Examiner US Cl. X.R. 8173, 178 

